A coepobation



Patented Feb. 3,1931 I 1T1:- 1.:

{QuNiTED STA- a .PATE

COMPANY, or MIDLAND, MICHIGAN, a; coaroaa'rrorr orrarcnrenu nmno'rmnvnnornn Azo ma mas v No Drawing.

This invention relatcsto azo dyestuffs and has regard particularly to clisazo dyes produced by tetrazotizing an aromatic diamine and coupling therewith a" suitable phenolic :ia or arylamine body.

In my pending application Serial No.

278,332, filed May 16, 1928, I have disclosed a methodof making azo dyestufls which consists essentially in tetrazotizing a diamlated to the type in question, but distin guished therefrom in that the dyes are com- 1 pletely insoluble in water. When such dyes are developed directly on the fibre, the dyed product possesses exceptional depth and clearness of color in various hues or shades of red, depending upon the particular components used for producing the dye, the colors being further characterized byextreme fastness to light and washing. The invention, then, consists of the steps and new products hereinafter fully described and particularly pointed out in the claims the following description setting forth but several of the various ways in which the prin- 1 general the dyes somade give colors ranging from scarlet-red to orange, yellow or brown. I have found, however, that when a diamino-diaryl ether is tetrazotized and coupled with naphthol A S, or similar arylides of 2.3 hydroxy-naphthoic acid, dyes of great clearness and brilliance are produced in characteristic shades chiefly of 'carmine and rose-red.

, EBNEsrfr. GRETHER, or MIDLAND, MICHIGAN,"essre rroa ro rii-n how cnnivrronr 7' Application filed March 7, 1929. sma t. 345,228. f. if,

'lThei dyes-of the general type comprised v by invention are constituted,according to r the following structural fOrmulaEW-herein R, Rffalid; R are .aryl residues .whichimay The procedure producing e11 developing these dyes will described' in thQ'ZfOh lowing illustrative example, it being under- Stood that similar"procedure may be 6111-. ployed equally well for ,otherdyes oif the present;'type.' V

" flatte material is "treated with an alkiline solution of naphthol A S so 'tliatuthe fibres are acompletely}timpregnatedv there-' with. A secondij-solution is prepared: by dissolving 20 parts diamino-diphenyl ether in dilute hydrochloric, acid, adding a solution 'containing 14 'parts sodium nitrite and then, adding'alkali until the solution isal- N most neutralized. The previously treated material is then immersed in the second solution in the cold. The dye is developed directly. onthefibre,-a brilliant'clear shade v of carininered, extremelyfast to light and .5 a

washing."

'Whilefa fast dyeing is radii; obtained withoutthe aid of mordants,th e use thereof is not precludedand' may be resorted to without departing from the spirit of the invention. 1 For instance, chrome mordanting produces, a distinct color modification in softer and less brilliant shades. Other mordants'or combinations thereof may be employed, if desired, such as Turkey red oil, metallic salts and the like, for creating "characteristiccolor tones or for other purposes, or

, similar fashion I have prepared other dyes of the same gene'raltype, asshown by the accompanying table, wherein the first column gives the particular arylide of 2.3-hydroxy-naphthoic, acid coupled with tetrazotizcd diamino-diphenyl ether and the second column the approximate color shade produced on 'the dyed material.

While in the example I have specifically referred to the cotton fibre as the material diphenyl ether coupled with 2.3-hydroxynaphthoic acid-anilide;

4. Material dyed with the dyestuii claimed in claim 1.

5. Material dyed with the dyestuficlaimed in'claim 2.

. 5.'-Material dyed withthe dyestufi' claimed in claim 3. Y

Signed by me this 4th day of March, 1929.

. ERNEST F. GRETHER- to be dyed, I may apply these Edyes to other textile fibres of vegetable. oranima'l origin, such as silk, or to synthetically prepared fibres, such as rayon or the like. Likewise I may employ, insteadof diaminodiphenyl ether, various nuclear substituted derivatives thereof, as the chlor-, brom-, nitro-, or other substituted derivatives, or I may employ other diamino-diaryl ethers, as, for example, diamino phenyl naphthylether, or a substituted derivative thereof.

' It is further within the purview of my in vention to prepare dyes of the presenttype in substance, as well as to prepare same in situ on the fibre. That is'tosa-y, the respective reaction components may be brought together directly, with or without the aid of a diluting or solvent medium, the dye being separated from the reaction mixture by any suitable means. Owing to the insolubility,,stability and fastness to light and water of such dye compounds, they are also valuable for use as pigments.

Other modes of applying the'principle of my invention may be employed instead of the one explained, change being made as regards the materials employed,provided the ingredients stated by any of the following claims or the equivalent of such stated ingredients be employed.

I therefore particularly point out'and distinctly claim as my invention 1. As anew product, an azo dyestuff composed of the tetrazotized product of adiamino-diaryl ether coupled with an arylide of 2.3-hydroxy-naphthoic acid.

2. As a new product, an azo posed of the tetrazotized product of diaminodiphenyl ether coupled with an arylide of 2.3 -hydroxy-naphthoic ac id.-

- 3. As anew product, an azo dyestuif composed of. the tetrazotized product ofdiamino- 

